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US20080099375A1 - Process for adsorption of sulfur compounds from hydrocarbon streams - Google Patents

Process for adsorption of sulfur compounds from hydrocarbon streams Download PDF

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Publication number
US20080099375A1
US20080099375A1 US11/977,898 US97789807A US2008099375A1 US 20080099375 A1 US20080099375 A1 US 20080099375A1 US 97789807 A US97789807 A US 97789807A US 2008099375 A1 US2008099375 A1 US 2008099375A1
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United States
Prior art keywords
adsorbent
sulfur
silica
support
nickel
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
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US11/977,898
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English (en)
Inventor
Miron Landau
Mordechay Herskowitz
Iehudit Reizner
Yaron Konra
Himanshu Gupta
Rajeev Agnihotri
Paul Berlowitz
James Kegerreis
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.)
ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Publication date
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Priority to US11/977,898 priority Critical patent/US20080099375A1/en
Priority to CA2667887A priority patent/CA2667887C/en
Priority to KR1020097010964A priority patent/KR101423353B1/ko
Priority to JP2009534695A priority patent/JP5033881B2/ja
Priority to CN2007800408377A priority patent/CN101678317B/zh
Priority to EP07839842.7A priority patent/EP2089154B1/en
Priority to PCT/US2007/022857 priority patent/WO2008054712A1/en
Publication of US20080099375A1 publication Critical patent/US20080099375A1/en
Priority to US12/799,120 priority patent/US8524071B2/en
Abandoned legal-status Critical Current

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    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/34—Regenerating or reactivating
    • B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • 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

  • the present invention provides a process for removing sulfur compounds from liquid hydrocarbon streams by using a high capacity adsorbent which is a composite material containing particles of nickel phosphide complex having a Ni/P ratio ranging from about 0.5:4, preferably about 2:3 and most preferably about 2.2:2.5.
  • the composite is preferably distributed in a phase containing silica, alumina or carbon, and obtained by reduction of composite material consisting of nickel phosphate (Ni 2 P 2 O 7 ), nickel oxide, and/or nickel hydroxide, ammonium phosphate ((NH 4 ) 2 HPO 4 ), wherein the composite material is preferably formed by deposition of nickel and phosphorus salts onto silica, mesoporous silica, silica-alumina or carbon materials.
  • the invention further includes using a sorbent where part of silica or carbon is removed from the said composite material after reduction increasing the loading of the nickel phosphide complex.
  • the process for desulfurization according to this invention is preferably a one-stage process that is carried out at temperature in range from 150° C. to 400° C., and it does not require a hydrogen enriched atmosphere.
  • the process can be carried out both in a batch mode and in a continuous mode.
  • the affinity of the adsorbent towards sulfur compounds enables ultra-deep desulfurization down to the levels of about 1 ppm and less.
  • the present invention can adsorb more than 1 g sulfur per 100 g of adsorbent.
  • the invention further enables periodic regeneration of the sorbent by removing the adsorbed sulfur in reductive atmosphere that increases the effective total sulfur capacity to more than about 2.0 g sulfur per 100 g.
  • the ultradeep desulfurization of liquid hydrocarbon fuels by adsorption of sulfur-organics without added hydrogen with a reasonable adsorbents sulfur capacity can be done using the two following processes—reactive adsorption of sulfur compounds with the sorbent containing metallic nickel (Ni°) deposited on a composite support converting Ni° to bulk nickel sulphide phases (as illustrated in US Patent Application 20050258077 A1, 2005) and by equilibrium adsorption of sulfur compounds with a zeolite sorbent containing partially reduced Cu(1+) cations (as illustrated by A. J. Hernandez-Maldonado, R. T. Yang, Ind. Eng. Chem. Res., 42, 123, 2003). Both processes suffer disadvantages relative to the present invention.
  • Ni° phase in the first process even at high nickel dispersion of >30% is limited by the tendency of Ni° to convert the existing unsaturated hydrocarbons in fuel to carbonaceous deposits. This leads to blocking of the sorbents surface at a faster rate than that needed for full conversion of Ni° phase to bulk nickel sulphides. This is also one of the reasons that the deactivated nickel sorbents cannot be regenerated by reductive treatment and oxidative regeneration techniques need to be employed to restore the material. Oxidative regeneration, i.e. burning out the carbonaceous deposits, converts the Ni° phase to poorly dispersed NiO phase.
  • Ni°-based sorbents yields very low sulfur capacity of less than 0.1 g per 100 g. This low capacity and sorbent non-regenerability substantially impairs the commercial application of such process for ultradeep desulfurization of diesel fuels.
  • the equilibrium adsorption process using Cu(1+) containing zeolite sorbents is generally limited to hydrocarbon feedstocks with relatively high sulfur contents of >50 ppm. At sulfur content in the feedstock ⁇ 20 ppm, which is the case for modern hydrotreated diesel fuels, the adsorption equilibrium established in this process at conventional temperatures does not reduce sulfur to below 1 ppm, as taught herein.
  • FIG. 1 shows XRD patterns of fresh and used NixP/SiO 2 .
  • FIG. 2 shows a reference sorbent activity
  • FIG. 3 shows sorbent activity for examples 2-4 of the present invention.
  • FIG. 4 shows sorbent activity for example 5 of the present invention
  • FIG. 5 shows regenerative and sorbent activity for an example of the present invention.
  • FIG. 6 shows sorbent performance on several diesel fuel samples varying in their boiling range and sulfur speciation
  • FIG. 7 shows sorbent performance as a function of LHSV.
  • FIG. 8 shows sorbent performance as a function of reaction temperature.
  • FIG. 9 shows the boiling point curves for feed and product diesel fuel.
  • FIG. 10 shows key bulk properties of feed and product diesel fuel.
  • the transition metal phosphide materials having the formula MP x , where M is selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta and W, x is between 0.1 and 10, and the material(s) are dispersed on a high surface area oxide support, are known catalysts for hydrodesulfurization of hydrocarbon feedstocks by converting the organo-sulfur compounds to H 2 S.
  • the present invention is based upon the discovery that select materials belonging to this group adsorb substantial amounts of organic sulfur from the hydrocarbon streams without added hydrogen.
  • the present invention includes a process for ultra-deep desulfurization of hydrotreated hydrocarbon liquid feedstocks, especially of diesel fuels.
  • One embodiment of the present invention is a nickel phosphide complex comprising 2-50 nm nanoparticles of the phases Ni 2 P, Ni 12 P 5 , Ni 3 P, or their mixtures thereof, that may be used as an active material for reactive adsorption of dibenzothiophene derivatives such as those existing in hydrotreated diesel fuels.
  • the metallic character of nickel in these compounds is believed to cause strong interaction of the lowest unoccupied molecular orbital (LUMO) of S-compound with valence bands of surface nickel atoms in NixP phase leading to the splitting of C—S bonds that shifts the adsorption equilibrium Ni x P+S—R ⁇ P ⁇ S—R . . .
  • Ni x P to the right. This permits reducing the feed sulfur content to less than 1 ppm even with inlet sulfur of about 20 ppm. Withdrawing a part of electron density from the nickel atoms by phosphorus in Ni x P phases imparts a partial positive charge (Ni ⁇ +) to nickel atoms, which decreases their ability to interact with electrophilic sulfur, depressing the formation of bulk Ni-sulphide phases.
  • the X-ray diffractograms of freshly reduced and spent, 30 wt. % Ni 12 P 5 /SiO 2 , after adsorption of 1.05 g sulfinur per 100 g material in desulfurization of a standard diesel fuel with 15 ppm sulfur content, are substantially identical as illustrated in FIG.
  • Ni x P based materials This indicates an absence of bulk nickel sulphide phases. Concurrently, a partial positive charge on nickel atoms in Ni x P phases is believed to reduce their ability to convert aromatic compounds into dense carbonaceous deposits, so that the amount of carbon deposits after a run does not exceed about 4-5 wt %.
  • the reductive treatment of spent Ni x P based materials allows removing the adsorbed sulfur from the surface of spent sorbent making it possible to conduct several sulfur adsorption cycles with the present invention using the same Ni x P-based material. This extends the total amount of sulfur that could be adsorbed by a batch of sorbent.
  • the adsorbent has high loading of disperse Ni x P complexes, ranging from about 15 st % to about 80 wt %, preferably 20 wt % to about 60 wt %.
  • the disperse Ni x P complexes have crystal sizes ranging from about 2 nanometers to about 50 nanometers (preferably 2-30 nm), and are deposited on silica, mesostructured silica, silica-alumina, carbon or a combination thereof with surface area ranging from about 200 m 2 /gm to about 800 m 2 /gm, and pore diameter ranging from about 5 nanometers to about 30 nanometers.
  • the material is prepared by reduction of nickel phosphate or nickel oxide (hydroxide) deposited on the mesoporous supports together with ammonium phosphate salt.
  • Impregnation of mesoporous supports i.e. silica or silica-alumina
  • One aspect of the present isnvention is increasing the Ni x P loading up to 60-80 wt. %.
  • increased load is accomplished by extraction of silica from reduced Ni x P/SiO 2 (SiO 2 —Al 2 O 3 ) composite material.
  • treating the reduced adsorbent with a solution of a strong base (NaOH) or aqueous HF at conditions that do not affect the composition of active Ni x P phase resulted in extraction of silica and consequently increased Ni x P loading.
  • the silica support material is preferentially “leached” out from the reduced adsorbent material, partially or completely, by the above mentioned chemical treatment.
  • high loading of active phase Ni x P may be obtained by implementation of homogeneous deposition-precipitation of highly dispersed NiO on mesoporous silica (silica-alumina) support from aqueous solution of Ni-salt in presence of urea at 50-80 wt. % Ni loading, as taught in co-pending US Patent Application 20050258077 A1, 2005, followed by deposition of (NH 4 ) 2 HPO 4 on the NiO/SiO 2 (SiO 2 —Al 2 O 3 ) material and reduction of so obtained material.
  • high loading of Ni x P phases may be obtained by implementation of homogeneous deposition-precipitation of highly dispersed nickel phosphate at 45-65% nickel loadings in presence of urea on mesoporous silica (silica-alumina) support from aqueous solution containing both Ni-salt and ammonium phosphate stabilized by nitric acid, followed by reduction of so obtained material.
  • the above mentioned embodiments are not limiting and there are potentially other techniques, as may be apparent to someone skilled in the art, of depositing fine crystalline Ni x P on a porous support.
  • the present invention is an adsorbent with desired loading of Ni x P (60-80%) and crystallite size (2-50 nm), surface area (200-800 m2/g) and pore size (5-30 nm).
  • the process of this invention for removing sulfur compounds from a liquid hydrocarbon stream comprises i) providing a composite material containing Ni 2 P, Ni 12 P 5 , Ni 3 P phases or their mixture as nanocrystals with 2-50 nm size and 20-80 wt. % loading stabilized in mesoporous silica, silica-alumina or carbon support matrix having surface area in range 200-800 m 2 /g and average pore diameter in range 5-30 nm; and ii) contacting said the liquid hydrocarbon stream with the adsorbent at temperature in range about 150-400° C., preferably in the range between 250 and 350° C.
  • the process is carried out without added hydrogen and it can be performed in a batch mode or in a continuous mode.
  • the liquid hour space velocity is chosen as to reach a required level of sulfur residue.
  • the LHSV is from about 0.5-30/hr, preferably from about 1-20/hr and most preferably from about 3-15/hr.
  • a preferred nickel content in the adsorbent that is used in the process of this invention is 20 wt. % to 80 wt. %, preferably from 25 wt. % to 70 wt. %, with the Ni/P atomic ratio from about 2 to about 3, preferably from about 2.2 to about 2.5.
  • the reduced composite material of the composition, crystal size of active nickel phosphide phases and matrix texture help to react with organo-sulfur compounds, especially dibenzothiophenes conventionally existing in liquid hydrocarbon streams such as hydrotreated diesel fuels to adsorb sulfur.
  • organo-sulfur compounds especially dibenzothiophenes conventionally existing in liquid hydrocarbon streams such as hydrotreated diesel fuels to adsorb sulfur.
  • the adsorbent used in the process according to present invention can be regenerated by reductive treatment, for example by exposing the adsorbent to hydrogen flow at about 450-600° C. This removes the adsorbed sulfur enabling further reuse of the sorbent at about the same adsorbent conditions reaching the same level of residual sulfur as in the first run.
  • the adsorbent can be successfully reused in several adsorption-regeneration cycles, yielding total effective sulfur capacity of >2 g sulfur per 100 g sorbent.
  • the Ni x P-based adsorbent described herein may be used for removing sulfur compounds from different hydrocarbon streams, where the hydrocarbon can comprise a material chosen from hydrotreated naphtha with added oxygenates for octane number improvement, diesel and jet fuels, alkanes, alkenes and aromatic hydrocarbons, and the sulfur compounds can comprise a material chosen from organic sulfides, organic disulfides, thiols, and aromatic compounds like thiophene, benzothiophene, dibenzothiophene and their derivatives.
  • the hydrocarbon can comprise a material chosen from hydrotreated naphtha with added oxygenates for octane number improvement, diesel and jet fuels, alkanes, alkenes and aromatic hydrocarbons
  • the sulfur compounds can comprise a material chosen from organic sulfides, organic disulfides, thiols, and aromatic compounds like thiophene, benzothiophene, dibenzothiophene and their derivatives.
  • silica gel (PROMEKS, PI-258) calcined at 500° C. for 2 h with surface area of 220 m 2 /g and pore diameter of 26 nm was placed with a mixture of two solutions 0.5 g aluminum tri-sec butoxide with 100 mL toluene, and 1.5 g triethylamine with 100 mL. The toluene suspension was vigorously stirred at 85° C. for 6 h, and then the solid was separated by filtration.
  • silica gel PROMEKS, PI-258
  • the alumina-grafted mesoporous silica solid was suspended in 150 mL of ethanol solution containing 0.22 g of water and it was stirred at room temperature for 24 h.
  • the alumina-grafted mesoporous silica solid then filtered and dried with vacuum at 85° C. for 2 h, followed by gradual calcinations in periods of 2 hours at temperatures 250° C. and 400° C. and then calcinated in air for 4 hours at 500° C.
  • the alumina-grafted mesoporous silica material exhibit surface area of 243 m 2 /g and a narrow mesopore size distribution, with the mean pore diameter of 5 nm and the pore volume of 0.3 cm 3 /g.
  • EDX analysis using a SEM Quanta 2000 Philips Fay Co. indicated the contents of Al, Si, and O to be 2.35, 50.32 and 47.35 wt %, respectively.
  • the mixture was stirred and heated at 90° C. for 24 hours. During this period, the pH increased to 6.4.
  • the mixture was quickly cooled to 20° C. on ice bath and filtered.
  • the solid was washed on filter with 200 ml of distilled water, and transferred into a flask with 200 ml of distilled water, stirred for 15 min at 60° C. and filtered again. This washing procedure was repeated twice.
  • the washed material was dried in air at 90° C. for 24 h and calcined at 500° C. for 4 h (the heating rate 5° C./min), which yielded 19.2 gram.
  • EDX analysis indicated the contents of Ni, Si, Al and O to be 63.47, 21.19, 1.3 and 14.04 wt %, respectively.
  • the surface area of the composite material, as measured by BET method, was 304 m 2 /g.
  • the above-obtained composite material was placed into a stainless steel reactor, having internal diameter 10 mm and length 100 mm, equipped with internal thermowell and heating oven.
  • the temperature controller maintained the temperature within ⁇ 1 degree C.
  • the adsorbent reduced at 450° C. in the stream of hydrogen at GHSV (gas hour space velocity) of 12000 h ⁇ 1 , for 8 hours then passivated in He flow and cooled in He to ambient temperature.
  • 0.5 g of the above composite material was reduced in a quartz reactor under atmospheric pressure with H 2 flux of 1000 cc*min ⁇ 1 g ⁇ 1 at 580° C. for 0.5 hour (amb. to 350° C. at 3.6° C./min and 350° C. to 580° C. at 1° C./min), then passivated in He flow and cooled to ambient temperature under He.
  • silica gel PROMEKS, PI-258
  • surface area 220 m 2 /g and pore diameter of 26 nm
  • the calcined silica wetness point was 2.7 cc (H 2 O)/g (silica) and the impregnation method was incipient wetness.
  • 0.5 g of the above composite material was reduced in a quartz reactor under atmospheric pressure with H 2 flux of 1000 cc*min ⁇ 1 g ⁇ 1 at 580° C. for 0.5 hour (amb. to 350° C. at 3.6° C./min and 350° C. to 580° C. at 1° C./min), then passivated in He flow and cooled to ambient temperature under He.
  • the total loading of these phases in BGU-4 material was 30 wt % based on EDX and XRD analysis.
  • a sample of 10 g of silica gel (DAVICAT, ID-2411) with surface area of 400 m 2 /g and average pore diameter of 8 nm was calcined at 550° C. for 2 hours. It was placed in the 250 ml flask inserted in a heating bath, provided by magnetic stirrer and condenser, that contained an aqueous solution prepared by dissolution of 93 g Ni(NO 3 ) 26 H 2 O, 84 g urea, 7 mL HNO 3 (70%) and 11.9 g (NH 4 ) 2 HPO 4 in 150 mL of H 2 O. The mixture was heated to 80° C. and stirred at this temperature for 24 hours. During this period, the pH increased from 0.96 to 5.
  • the mixture was cooled to room temperature and filtered.
  • the solid was transferred into a flask with 200 mL of distilled water at 60° C., stirred for 1.5 min and filtered again. This washing procedure was repeated twice.
  • the washed material was dried at 120° C. for 4 hours (the heating rate 5° C./min) and calcined in air at 500° C. for 6 hours (the heating rate 1° C./min).
  • EDX analysis performed by the instrument SEM Quanta 2000 Philips Fay Co., indicated the contents of Ni, P, Si, and O to be 62.8, 13.1, 6.4 and 17.6 wt. %, respectively.
  • the surface area of the composite material was 175 m 2 /g.
  • 0.5 g of the above composite material was reduced in a quartz reactor under atmospheric pressure with H 2 flux of 1000 cc*min ⁇ 1 g ⁇ 1 at 580° C. for 0.5 hour (amb. to 350° C. at 3.6° C./min and 350° C. to 580° C. at 1° C./min), then passivated in He flow and cooled to ambient temperature under He.
  • the total loading of these phases in BGU-5 material was 62.2 wt. % based on EDX and XRD analysis.
  • the surface area of the reduced BGU-5 material was 205 m 2 /g.
  • a sample of 0.8 g of the BGU sorbent material prepared according to examples 1-5 after calcination in air was placed into a tubular stainless steel reactor, having internal diameter of 5 mm and length of 10 cm, equipped with internal thermowell and heating oven.
  • the temperature controller was used to maintain temperature within ⁇ 1° C.
  • the adsorbent was reduced under atmospheric pressure with H 2 flux of 1000 cc*min ⁇ 1 g ⁇ 1 at 580° C. for 0.5 h (amb. to 350° C. at 3.6° C./min and 350° C. to 580° C. at 1° C./min), and cooled under H 2 flow to the reaction temperature of 300° C.
  • the hydrotreated diesel fuel with IBP 193° C.
  • the testing results of the BGU-1 reference material containing metallic nickel phase are shown in FIG. 2 .
  • the nickel phase in this sorbent is not active enough in order to remove the sulfur from diesel fuel at selected space time (contact time) to less than 1 ppm.
  • the S out was 3 ppm wt. and slowly rose during about 50 h to ⁇ 8 ppm wt.
  • the testing results of BGU-2, BGU-3 and BGU-4 sorbents containing different nickel phosphide phases are presented in FIG. 3 .
  • All the materials displayed high activity meaning sulfur adsorption rate high enough to yield S out . ⁇ 0.1 ppm.wt at selected contact time.
  • the EDX analysis of spend sorbents gave, respectively 0.67; 1.02 and 0.88 wt. % of sulfur.
  • the patterns of XRD diffractograms of spend sorbents were substantially identical to that of fresh samples after hydrogen reduction that are shown in FIG. 1 .
  • the testing results of BGU-5 sorbent with enhanced nickel phosphide phases loading of 62.2 wt. % are presented in FIG. 4 .
  • the material displayed high activity meaning sulfur adsorption rate high enough to yield S out . ⁇ 0.5 ppm.wt at selected contact time of 2.7 h ⁇ 1 .
  • the total sulfur capacity obtained for BGU-5 sorbent in run stopped when the S out value exceeded 0.5 ppm wt. was ⁇ 1.5 g per 100 g of sorbernt.
  • the EDX analysis of spend sorbent gave 1.6 wt. % of sulfur.
  • the liquid pump was stopped when sulfur content in the treated diesel fuel S out reached 0.2 ppm wt.
  • the pressure in reactor was reduced to atmospheric and the temperature increased to 550° C. (heating rate 1° C./min) under H 2 flux of 1000 cc*min ⁇ 1 g ⁇ 1 , and kept at 550° C. for 3.5 hours making the reductive regeneration of the sorbent.
  • the reactor then was cooled down to the reaction temperature 300° C. under H 2 flow, then purged with He and the pressure of He was increased to 17 bar.
  • sorbent of the present invention removes a range of sulfur compounds (mercaptans, sulfides, disulfides, thiophenes, benzothiphenes (BT), dibenzothiophenes (DBT) and substituted DBTs) from hydrocarbon fuel mixtures.
  • sulfur compounds mercaptans, sulfides, disulfides, thiophenes, benzothiphenes (BT), dibenzothiophenes (DBT) and substituted DBTs
  • a variety of diesel fuel samples were subjected to desulfurization by the BGU-4 sorbent. These diesel fuel samples differed in total sulfur concentration and in the type of sulfur speciation. For example, Diesel A (boiling range: 136-387° C.) is characterized by 11 ppm total sulfur. However, refractory sulfur compounds (DBTs and higher) accounts for only 1 ppm in this sample.
  • Diesel B was obtained by adding 4,6-dimethyl-DBT to Diesel A to raise the total sulfur concentration to 14.3 ppm.
  • Diesel C (boiling range: 107-362° C.) is a relatively higher boiling fraction that is blended with lighter boiling fractions to make the final diesel fuel.
  • the sulfur speciation in Diesel C is dominated by refractory sulfur compounds. Over 94% of the sulfur is more refractory than DBT, with 76% being more refractory than 4,6-dimethyl-DBT. Additionally, 50% of the sulfur compounds are heavier than 4,6-diethyl-DBT.
  • Diesel D (boiling range: 127-336° C.) is a sample of unadditized full range diesel typically sold in the European market.
  • the desulfurization was carried out at a LHSV of 6/hr at 300° C. and under 250 psig pressure in a reactor containing 6 cm 3 sorbent.
  • the results are shown in FIG. 6 .
  • the sorbent BGU-3 is capable of achieving sub-ppm desulfurization on a variety of diesel fuel samples, differing in their boiling range and sulfur speciation.
  • BGU-3 extracts sulfur atoms from a variety of organo-sulfur compounds, including refractory sulfur compounds that are hard to remove by conventional hydrodesulfurization processes.
  • BGU-4 sorbent maintains its reactivity (wt % sulfur capture) over a range of fuel flowrate.
  • the influence of varying flowrate (liquid hourly space velocity or LHSV) on the sorbent reactivity was quantified in a 6 cm 3 fixed bed reactor operated at 300° C. and 250 psig. These experiments were carried out with Diesel B, detailed in Example 8 above.
  • the data presented in FIG. 7 shows that the breakthrough fuel volumes processed (measured at an exit S concentration of 1 ppm) do not change appreciably in the range of LHSV tested.
  • BGU-4 is able to maintain its reactivity over a large turndown ratio. This facilitates application of this desulfurization process in inherently transient operation, such as on-board a vehicle.
  • a high LHSV operation enables the usage of this sorbent in space constrained environment.
  • BGU-4 maintains its reactivity over a wide temperature range.
  • the influence of reaction temperature on the sorbent reactivity was quantified in a 6 cm 3 fixed bed reactor operated at 6/hr LHSV and 250 psig. These experiments were carried out with Diesel B, detailed in Example 8 above.
  • the data presented in FIG. 8 demonstrates that sub-ppm desulfurization is attained in the tested temperature range of 275-350° C.
  • the wt % S capture by the sorbent does not indicate a sharp maximum in this temperature range either.
  • This robustness of the sorbent to reaction temperature would be especially beneficial to transient operations, such as the sub-ppm desulfurization of diesel fuel (containing 10-50 ppm total sulfinur) on-board a vehicle.
  • the desulfurization process does not significantly change the properties of the resulting desulfurized fuel, thereby helping ensure that the lower sulfur fuel product meets fuel specifications.
  • the following tests were carried out on Diesel A sample that was desulfurized at 300° C., 250 psig and 6/hr LHSV using BGU-4 adsorbent. As shown in FIG. 9 , there is no appreciable change in the boiling range of Diesel A and sub-ppm sulfur product of Diesel A as a result of this desulfurization process (ASTM D86-01).

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070262025A1 (en) * 2006-03-31 2007-11-15 Perry Equipment Corporation Canister for treatment of contaminated fluids
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US20080128364A1 (en) * 2006-12-01 2008-06-05 Dan Cloud Filter element and methods of manufacturing and using same
US20080135454A1 (en) * 2006-12-06 2008-06-12 Saudi Arabian Oil Company Composition and process for the removal of sulfur from middle distillate fuels
US20090032472A1 (en) * 2007-07-31 2009-02-05 Perry Equipment Corporation Systems and methods for removal of heavy metal contaminants from fluids
US20090107882A1 (en) * 2007-10-30 2009-04-30 Ying Zheng Adsorbents for denitrogenation desulfurization of hydrocarbon oils and methods of producing
US20090145808A1 (en) * 2007-11-30 2009-06-11 Saudi Arabian Oil Company Catalyst to attain low sulfur diesel
US20090159531A1 (en) * 2006-03-31 2009-06-25 Krogue John A Composite adsorbent block for the treatment of contaminated fluids
US20090230026A1 (en) * 2008-02-21 2009-09-17 Saudi Arabian Oil Company Catalyst To Attain Low Sulfur Gasoline
US20100282567A1 (en) * 2009-05-08 2010-11-11 Krishnan Sankaranarayanan On-board desulfurization system
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US20110084002A1 (en) * 2008-12-15 2011-04-14 Anshu Nanoti Process for the removal of sulfones from oxidized hydrocarbon fuels
US20110220547A1 (en) * 2010-03-15 2011-09-15 Abdennour Bourane Targeted desulfurization process and apparatus integrating oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds
US20110220550A1 (en) * 2010-03-15 2011-09-15 Abdennour Bourane Mild hydrodesulfurization integrating targeted oxidative desulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds
US8142646B2 (en) 2007-11-30 2012-03-27 Saudi Arabian Oil Company Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds
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US20130330555A1 (en) * 2012-06-06 2013-12-12 Exxonmobil Research And Engineering Company Novel adsorbent for ultradeep removal of sulfur compounds from distillate fuels
US20140018455A1 (en) * 2012-07-05 2014-01-16 Yunjie Ding Phosphide Catalyst for Syngas Conversion and the Production Method and Use thereof
US8906227B2 (en) 2012-02-02 2014-12-09 Suadi Arabian Oil Company Mild hydrodesulfurization integrating gas phase catalytic oxidation to produce fuels having an ultra-low level of organosulfur compounds
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US11669819B2 (en) 2009-10-13 2023-06-06 Block, Inc. Automatic storage of electronic receipts across merchants and transaction cards
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4740360A (en) * 1985-11-11 1988-04-26 Harshaw Chemie B.V. Process for preparing supported catalyst systems
US20060142150A1 (en) * 2004-12-24 2006-06-29 Jongheop Yi Method of preparing a platinum catalyst for use in fuel cell electrode

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0620539B2 (ja) * 1986-12-02 1994-03-23 日本化薬株式会社 脱臭剤
JP3029841B2 (ja) * 1990-04-16 2000-04-10 株式会社豊田中央研究所 複合吸着材およびその製造方法
AU7725200A (en) * 1999-09-30 2001-04-30 Virginia Tech Intellectual Properties, Inc. Novel transition metal phosphide catalysts
US6429170B1 (en) * 2000-05-30 2002-08-06 Phillips Petroleum Company Sorbents for desulfurizing gasolines and diesel fuel
WO2003068892A2 (en) * 2002-02-12 2003-08-21 The Penn State Research Foundation Deep desulfurization of hydrocarbon fuels
US7074324B2 (en) * 2002-06-05 2006-07-11 Exxonmobil Research And Engineering Company Process to remove sulfur contaminants from hydrocarbon streams

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4740360A (en) * 1985-11-11 1988-04-26 Harshaw Chemie B.V. Process for preparing supported catalyst systems
US20060142150A1 (en) * 2004-12-24 2006-06-29 Jongheop Yi Method of preparing a platinum catalyst for use in fuel cell electrode

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8142664B2 (en) 2006-03-31 2012-03-27 Perry Equipment Corporation Method for treatment of contaminated fluids
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US20090159531A1 (en) * 2006-03-31 2009-06-25 Krogue John A Composite adsorbent block for the treatment of contaminated fluids
US20070262025A1 (en) * 2006-03-31 2007-11-15 Perry Equipment Corporation Canister for treatment of contaminated fluids
US7662291B2 (en) * 2006-03-31 2010-02-16 Perry Equipment Corporation Canister for treatment of contaminated fluids
US7718071B2 (en) 2006-03-31 2010-05-18 Perry Equipment Corporation Treatment of contaminated fluids
US20100140176A1 (en) * 2006-03-31 2010-06-10 Perry Equipment Corporation Canister for Treatment of Contaminated Fluids
US20080128364A1 (en) * 2006-12-01 2008-06-05 Dan Cloud Filter element and methods of manufacturing and using same
US8499939B2 (en) 2006-12-01 2013-08-06 Perry Equipment Corporation Filter element and methods of manufacturing and using same
US8845899B2 (en) 2006-12-01 2014-09-30 Pecofacet (Us), Inc. Filter element and methods of manufacturing and using same
US8062523B2 (en) 2006-12-01 2011-11-22 Perry Equipment Corporation Filter element and methods of manufacturing and using same
US8293106B2 (en) 2006-12-01 2012-10-23 Perry Equipment Corporation Filter element and methods of manufacturing and using same
US8323480B2 (en) 2006-12-06 2012-12-04 Saudi Arabian Oil Company Composition and process for the removal of sulfur from middle distillate fuels
US7842181B2 (en) * 2006-12-06 2010-11-30 Saudi Arabian Oil Company Composition and process for the removal of sulfur from middle distillate fuels
US20110024330A1 (en) * 2006-12-06 2011-02-03 Saudi Arabian Oil Company Composition and Process for the Removal of Sulfur from Middle Distillate Fuels
US20080135454A1 (en) * 2006-12-06 2008-06-12 Saudi Arabian Oil Company Composition and process for the removal of sulfur from middle distillate fuels
US20090032472A1 (en) * 2007-07-31 2009-02-05 Perry Equipment Corporation Systems and methods for removal of heavy metal contaminants from fluids
US20090107882A1 (en) * 2007-10-30 2009-04-30 Ying Zheng Adsorbents for denitrogenation desulfurization of hydrocarbon oils and methods of producing
US7935248B2 (en) * 2007-10-30 2011-05-03 The University Of New Brunswick Adsorbents for denitrogenation desulfurization of hydrocarbon oils and methods of producing
US20090145808A1 (en) * 2007-11-30 2009-06-11 Saudi Arabian Oil Company Catalyst to attain low sulfur diesel
US8142646B2 (en) 2007-11-30 2012-03-27 Saudi Arabian Oil Company Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds
US10596555B2 (en) 2008-02-21 2020-03-24 Saudi Arabian Oil Company Catalyst to attain low sulfur gasoline
US10252247B2 (en) 2008-02-21 2019-04-09 Saudi Arabian Oil Company Catalyst to attain low sulfur gasoline
US9636662B2 (en) 2008-02-21 2017-05-02 Saudi Arabian Oil Company Catalyst to attain low sulfur gasoline
US20090230026A1 (en) * 2008-02-21 2009-09-17 Saudi Arabian Oil Company Catalyst To Attain Low Sulfur Gasoline
US8562821B2 (en) * 2008-12-15 2013-10-22 Council of Scientific & Industrial Research Center for High Technology Process for the removal of sulfones from oxidized hydrocarbon fuels
US20110084002A1 (en) * 2008-12-15 2011-04-14 Anshu Nanoti Process for the removal of sulfones from oxidized hydrocarbon fuels
WO2010129453A1 (en) * 2009-05-08 2010-11-11 Exxonmobil Research And Engineering Company On-board desulfurization system
US20100282567A1 (en) * 2009-05-08 2010-11-11 Krishnan Sankaranarayanan On-board desulfurization system
US11669819B2 (en) 2009-10-13 2023-06-06 Block, Inc. Automatic storage of electronic receipts across merchants and transaction cards
US9644156B2 (en) 2010-03-15 2017-05-09 Saudi Arabian Oil Company Targeted desulfurization apparatus integrating oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds
US20110220550A1 (en) * 2010-03-15 2011-09-15 Abdennour Bourane Mild hydrodesulfurization integrating targeted oxidative desulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds
US9296960B2 (en) 2010-03-15 2016-03-29 Saudi Arabian Oil Company Targeted desulfurization process and apparatus integrating oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds
US20110220547A1 (en) * 2010-03-15 2011-09-15 Abdennour Bourane Targeted desulfurization process and apparatus integrating oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds
US9005432B2 (en) 2010-06-29 2015-04-14 Saudi Arabian Oil Company Removal of sulfur compounds from petroleum stream
CN101979141B (zh) * 2010-09-15 2012-08-22 天津大学 改性的磷化镍催化剂及其用于氯苯类化合物加氢脱氯的方法
CN101979141A (zh) * 2010-09-15 2011-02-23 天津大学 改性的磷化镍催化剂及其用于氯苯类化合物加氢脱氯的方法
US8535518B2 (en) 2011-01-19 2013-09-17 Saudi Arabian Oil Company Petroleum upgrading and desulfurizing process
US9951283B2 (en) 2011-01-19 2018-04-24 Saudi Arabian Oil Company Petroleum upgrading and desulfurizing process
US8939014B2 (en) 2011-04-06 2015-01-27 Exxonmobil Research And Engineering Company Identification and use of an isomorphously substituted molecular sieve material for gas separation
US8906227B2 (en) 2012-02-02 2014-12-09 Suadi Arabian Oil Company Mild hydrodesulfurization integrating gas phase catalytic oxidation to produce fuels having an ultra-low level of organosulfur compounds
US20130330555A1 (en) * 2012-06-06 2013-12-12 Exxonmobil Research And Engineering Company Novel adsorbent for ultradeep removal of sulfur compounds from distillate fuels
US8877153B2 (en) * 2012-06-06 2014-11-04 Exxonmobil Research And Engineering Company Adsorbent for ultradeep removal of sulfur compounds from distillate fuels
EP2803406A4 (en) * 2012-07-05 2015-01-21 Dalian Chemical Physics Inst PHOSPHIDE CATALYST FOR THE CONVERSION OF SYNTHESEGAS, METHOD OF MANUFACTURING THEREOF AND USE THEREOF
US9120719B2 (en) * 2012-07-05 2015-09-01 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Phosphide catalyst for syngas conversion and the production method and use thereof
US20140018455A1 (en) * 2012-07-05 2014-01-16 Yunjie Ding Phosphide Catalyst for Syngas Conversion and the Production Method and Use thereof
CN102911003A (zh) * 2012-10-26 2013-02-06 山西阳煤丰喜肥业(集团)有限责任公司 一种脱除焦化苯中噻吩硫的方法
US8920635B2 (en) 2013-01-14 2014-12-30 Saudi Arabian Oil Company Targeted desulfurization process and apparatus integrating gas phase oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds
US11995624B2 (en) 2016-03-15 2024-05-28 Block, Inc. System-based detection of card sharing and fraud
US10410200B2 (en) 2016-03-15 2019-09-10 Square, Inc. Cloud-based generation of receipts using transaction information
US10628811B2 (en) 2016-03-15 2020-04-21 Square, Inc. System-based detection of card sharing and fraud
US11151531B2 (en) 2016-03-15 2021-10-19 Square, Inc. System-based detection of card sharing and fraud
US10636019B1 (en) 2016-03-31 2020-04-28 Square, Inc. Interactive gratuity platform
US11935016B2 (en) 2016-03-31 2024-03-19 Block, Inc. Interactive gratuity platform
US11436578B2 (en) 2016-03-31 2022-09-06 Block, Inc. Interactive gratuity platform
US10752847B2 (en) 2017-03-08 2020-08-25 Saudi Arabian Oil Company Integrated hydrothermal process to upgrade heavy oil
US11149216B2 (en) 2017-03-08 2021-10-19 Saudi Arabian Oil Company Integrated hydrothermal process to upgrade heavy oil
US11149218B2 (en) 2017-03-14 2021-10-19 Saudi Arabian Oil Company Integrated supercritical water and steam cracking process
US10703999B2 (en) 2017-03-14 2020-07-07 Saudi Arabian Oil Company Integrated supercritical water and steam cracking process
US10526552B1 (en) 2018-10-12 2020-01-07 Saudi Arabian Oil Company Upgrading of heavy oil for steam cracking process
US11230675B2 (en) 2018-10-12 2022-01-25 Saudi Arabian Oil Company Upgrading of heavy oil for steam cracking process
US10975317B2 (en) 2018-10-12 2021-04-13 Saudi Arabian Oil Company Upgrading of heavy oil for steam cracking process
WO2022144562A1 (en) * 2020-12-28 2022-07-07 Totalenergies Onetech Recovery method of organic molecules from a complex matrix
US12492348B2 (en) 2020-12-28 2025-12-09 Université de Pau et du Pays de l'Adour Recovery method of organic molecules from a complex matrix
US20240042382A1 (en) * 2021-02-19 2024-02-08 Nissan Chemical America Corporation Use of silica nanoparticles with glyoxal for h2s scavenging

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