WO2016065253A1 - Synthèse d'un catalyseur à base de sulfure de molybdène (mos2) et de sulfure de tungstène (ws2) - Google Patents

Synthèse d'un catalyseur à base de sulfure de molybdène (mos2) et de sulfure de tungstène (ws2) Download PDF

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Publication number
WO2016065253A1
WO2016065253A1 PCT/US2015/057099 US2015057099W WO2016065253A1 WO 2016065253 A1 WO2016065253 A1 WO 2016065253A1 US 2015057099 W US2015057099 W US 2015057099W WO 2016065253 A1 WO2016065253 A1 WO 2016065253A1
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WIPO (PCT)
Prior art keywords
catalyst
precursor
ammonium
sulfur
sulfide
Prior art date
Application number
PCT/US2015/057099
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English (en)
Inventor
Juan LEAL
Russell Chianelli
Jason Parsons
Brenda Torres
Maryam Zarei CHALESHTORI
Jacob SOLLNER
Original Assignee
Leal Juan
Russell Chianelli
Jason Parsons
Brenda Torres
Chaleshtori Maryam Zarei
Sollner Jacob
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Application filed by Leal Juan, Russell Chianelli, Jason Parsons, Brenda Torres, Chaleshtori Maryam Zarei, Sollner Jacob filed Critical Leal Juan
Publication of WO2016065253A1 publication Critical patent/WO2016065253A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/06—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • Molybdenum sulfide (MoS 2 ) and tungsten sulfide (WS 2 ) based catalysts can be used for a hydrotreating process.
  • the petroleum industry is increasingly turning to dirty feeds such as, coal, tar sands, heavy crudes, and residues as sources for future feedstocks. Feedstocks derived from these materials contain more sulfur, nitrogen, and aromatics than conventional crude oils, and thus require a considerable amount of refining in order to obtain usable products.
  • Hydrotreating removes unwanted compounds/elements (sulfur, nitrogen, aromatics) and includes reactions such as hydrodesulfurization, hydrodenitrogenation, and hydrogenating.
  • hydrodesulfurization reaction sulfur compounds are hydrogenated and cracked - carbon-sulfur bonds are broken and the sulfur is converted to hydrogen sulfide and removed from the process as a gas.
  • hydrodenitrogenation carbon-nitrogen bonds are broken, and the nitrogen is converted to ammonia and is similarly removed from the process as a gas.
  • unsaturated hydrocarbons and aromatics are reduced and hydrogenated.
  • a higher catalyst surface area results in higher catalytic activity.
  • synthesizing or developing a Mo and W sulfide catalyst, or Mo and W sulfide-based catalyst with higher surface area is desirable.
  • Alumina supported Mo and W sulfides mixed with divalent cobalt (Co) or nickel (Ni) sulfides can be used as the hydrotreating catalyst by the petroleum industry.
  • Certain embodiments are directed to a C0M0S 2 catalyst prepared by one or more steps selected from: (a) adding cobalt nitrate hexahydrate and ammonium molybdate to an ammonium hydroxide solution, (b) adding sulfur to form a reaction mixture, (c) refluxing the reaction mixture to form a CoMoS 2 catalyst precursor, (d) cooling the refluxed reaction mixture, (e) separating C0M0S 2 catalyst precursor from the reaction mixture, (f) washing the CoMoS 2 catalyst precursor filtrate with water, (g) washing the C0M0S 2 precursor with acetone followed by air drying, and (h) decomposing the C0M0S 2 catalyst precursor at a temperature above 300°C to form C0M0S 2 catalyst.
  • molybdenum trioxide is substituted for ammonium molybdate as a starting molybdenum source.
  • the starting molar ratio of Co to Mo is 0.25: 1, 0.5: 1, 0.75: 1 and 1 :1 including all values and ranges there between.
  • the sulfur to molybdenum molar ratio in the reaction mixture is about 2: 1, 3: 1, 4:1, 5: 1, or 6:1.
  • decomposition of the CoMoS 2 catalyst precursor is performed in a tube furnace under flowing 5% H 2 in 95% Ar gas mixture, resulting in formation of a CoMoS 2 catalyst.
  • the precursor is held constant at 450°C for 1 hour and then cooled to room temperature.
  • the decomposition of the precursor can be performed under a constant gas flow of about 25, 50, 100, 150, or 200 ml/min.
  • Certain embodiments are directed to a CoWS 2 catalyst prepared by one or more of the following steps (a) adding cobalt nitrate hexahydrate and ammonium tungstate to an ammonium hydroxide solution, (b) adding sulfur to the reaction mixture, (c) refluxing the reaction mixture at an elevated temperature followed by cooling, (d) separating CoWS 2 precursors from the reaction mixture through filtration, (e) washing the CoWS 2 precursor filtrate with water to remove any soluble impurities, (f) washing the CoWS 2 precursor with acetone followed by air drying, (g) decomposing the CoWS 2 precursor at an elevated temperature above 300°C to form CoWS 2 based catalyst.
  • the starting molar ratio of Co to W is 0.25: 1, 0.5: 1, 0.75: 1 and 1 : 1 including all values and ranges there between.
  • 4 fold more moles of sulfur with respect of W is added to the reaction mixture.
  • decomposition of WS 2 precursor is performed in a tube furnace using 5% H 2 in 95% Ar gas mixture resulting in the formation of CoWS 2 based catalyst.
  • the precursor is held at 450°C for 1 hour and then cooled to room temperature. The decomposition of the precursor can be performed under a constant gas flow of about 100 ml/min.
  • Certain embodiments are directed to modified asphaltene supported MoS 2 catalyst prepared by adding modified asphaltene to a solution of (NH 4 ) 6 Mo 7 0 2 4, 4H 2 0, followed by drying at an elevated temperature.
  • FIG. 1 Other embodiments are directed to carbon nanotube supported MoS 2 catalyst prepared by steps comprising of adding carbon nanotube to a solution of (NH 4 ) 6 Mo 7 0 24 , 4H 2 0, followed by drying at an elevated temperature.
  • carbon nanotubues are coaxial cylinders of graphite sheets, generally having a diameter of about 0.5 nanometers to about 100 nanometers. It is a nanomaterial composed of sp 2 -bonded carbon atoms. Carbon nanotubes can be in particulate or powder forms.
  • FIG. 1 MoS 2 catalytic structure.
  • FIG. 3 Removal of dibenzothiophene from decahydronapthalene solution using the CoMoS 2 catalyst.
  • Transition metal sulfides are the optimal catalysts to carry out hydrogenation and hydrogeno lysis.
  • Unsupported transition metal sulfide catalysts have been prepared by different methods, including co-maceration and homogeneous sulfide precipitation.
  • Embodiments described herein are directed to low cost methods of producing transition metal sulfides using sulfur zero.
  • Transition metal sulfides contain heteroatoms, transition metals, and sulfur. The transition metal sulfides can be used as supported or unsupported catalyst to change selectivity and enhance catalytic activities, having a high impact in hydrodesulfurization and hydrogenation capabilities.
  • any type of starting reactant such as, for example, cobalt ammonium nitrate hexahydrate and ammonium molybdate or ammonium tungstate, in a molar ratio of 0.1, 0.25, 0.50, 0.75, or 1 to 1 (cobalt ammonium nitrate hexahyudrate: ammonium molybdate) are added to a 25-30% (weight/volume) ammonium hydroxide solution.
  • Sulfur in an amount that is 2, 3, 4, or 5 times the amount of ammonium molybdate or ammonium tungstate on a per mole basis is added to the reaction mixture.
  • the reactants can be cobalt nitrate (Co(N0 3 ) 2 ) hexahydrate and molybdenum trioxide (M0O 3 ) at about 1 : 1 molar ratio in conjunction with a molar ratio of sulfur to molybdenum of about 4: 1.
  • the reactants are added to a round bottom flask or other appropriate vessel.
  • the reaction mixture is then refluxed with constant stirring to produce a catalyst precursor.
  • the reaction mixture is refluxed for 2, 3, 4, 5, 6, 7, 8, 9, 10 or more hours. After sufficient time refluxing the catalyst precursor is isolated from the reaction mixture.
  • the reaction mixture is cooled after refluxing.
  • the catalyst precursor is isolated by filtration with the catalyst precursor being retained on the filter.
  • a filter or its equivalent can be used
  • the catalyst precursor is then washed with an aqueous solution (e.g., water) to remove unreacted starting material and soluble byproducts.
  • the catalyst precursor is then washed with acetone and dried.
  • the catalyst precursor is then decomposed in a tube furnace.
  • the decomposition reaction is performed under about 1 atmosphere of pressure or other possible ranges for pressure.
  • the decomposition is in the presence or a 5% H 2 in 95% Ar gas mixture, for example.
  • the catalyst precursor is incubate at 300, 350, 400, 450, 500, 550 or 600°C for 1, 2, 3, 4, 5 or more hours under a constant gas flow of about 25, 50, 100, 125, 150, 200 ml/min.
  • the decomposed product is then cooled to room temperature.
  • the catalyst produced by the methods described herein can be used in conjunction with a carbon support.
  • the carbon support can be an asphaltene support or a carbon nanotube support.
  • the catalysts produced by the methods described herein may be used in a variety of reactions or may be further processed.
  • the catalyst is used in a hydrotreating processes, including those used in the petrochemical field.
  • Cobalt ammonium nitrate hexahydrate and ammonium molybdate are added to a round bottom flask containing 100 mL of 25-30% (weight/volume) ammonium hydroxide solution.
  • cobalt ammonium nitrate hexahydrate and ammonium molybdate are added to the flask.
  • sulfur is added to the reaction flask.
  • the reaction mixture is then refluxed for 5 hours under constant stirring to produce CoMoS 2 precursor. After refluxing, the reaction is cooled to room temperature. CoMoS 2 precursor is filtered out of the cooled solution.
  • the CoMoS 2 precursor is then washed with water twice, removing any unreacted starting material and any soluble byproducts.
  • the precursor is then washed with acetone and dried.
  • the precursor is then decomposed in a tube furnace in the presence or a 5% H 2 in 95% Ar gas mixture.
  • the precursor is decomposed by incubating the precursor at 450°C for 1 hour under a constant gas flow of 100 ml/min.
  • the decomposed product is then cooled to room temperature.
  • Cobalt ammonium nitrate hexahydrate and ammonium tungstate are added to a round bottom flask containing 100 mL of 25-30% (weight/volume) ammonium hydroxide solution. Subsequent to the addition of the cobalt and tungsten compounds, sulfur is added to the reaction flask. The reaction mixture was then refluxed for 5 hours under constant stirring. After refluxing, the samples were cooled to room temperature. CoWS 2 precursor is collected by filtration. The CoWS 2 precursor is then washed with water twice to remove any unreacted starting material and any soluble byproducts formed during the reaction. The sample is then washed with acetone and dried.
  • the synthesized precursor is then decomposed in a tube furnace using a 5% H 2 in 95% Ar gas mixture.
  • the samples are held constant at 450°C for 1 hour and then cooled to room temperature.
  • the decomposition of the precursor was performed under a constant flowing gas condition, of 100 ml/min.
  • Catalytic testing was performed using standard testing conditions for the model DBT reaction.
  • the reactor was sealed and then purged twice with H 2 gas to remove other gases from the mixture and refilled at 160 psi of H 2 gas.
  • the samples were collected and cooled to room temperature, the samples were analyzed using a Perkin Elmer Auto system XL gas chromatography systems connected to a Turbomass gold mass spectrometer.
  • the operational parameters of the GCMS system were as follows: Injector Temperature 260°C, Oven temperature initial 40°C, hold time 1 minute, final Temperature 260°C (hold time 5 minutes), ramp rate 20°C/min, gas flow 0.3 mL/min.
  • the mass spectrometer was used in scanning mode from intimal m/Z of 18 to 220. The different products were identified using the Mass spectra of the solution.
  • the removal rates for the DBT were determined using the integrated areas of the samples collected at different times. All analysis were performed in triplicate for statistical purposes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Catalysts (AREA)

Abstract

Cette invention concerne un catalyseur à base de CoWS2 ou de CoMoS2 préparé par chauffage à reflux de réactifs pour former un matériau précurseur qui est ensuite décomposé pour former un catalyseur. Plus spécifiquement, un catalyseur à base de CoMoS2 préparé à partir de nitrate-hexahydrate de cobalt et de molybdate d'ammonium pour former un précurseur de catalyseur CoMoS2 qui est ensuite décomposé pour former un catalyseur CoMoS2 est décrit.
PCT/US2015/057099 2014-10-23 2015-10-23 Synthèse d'un catalyseur à base de sulfure de molybdène (mos2) et de sulfure de tungstène (ws2) WO2016065253A1 (fr)

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US201462067474P 2014-10-23 2014-10-23
US62/067,474 2014-10-23

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WO2016065253A1 true WO2016065253A1 (fr) 2016-04-28

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106238073A (zh) * 2016-07-15 2016-12-21 温州泓呈祥科技有限公司 一种MoS2/LDHS加氢脱硫催化剂的制备方法及应用
CN106238074A (zh) * 2016-07-15 2016-12-21 温州泓呈祥科技有限公司 一种Pt‑MoS2/LDHS加氢裂化催化剂的制备方法及应用
CN106277056A (zh) * 2016-07-27 2017-01-04 广东工业大学 一种氧掺杂MoS2纳米花的制备方法
CN114345374A (zh) * 2020-09-27 2022-04-15 武汉理工大学 一种碳布上构筑的非晶态多硫化钼析氢电催化剂的制备方法
CN114835163A (zh) * 2022-05-24 2022-08-02 南京邮电大学 一种面向水质净化的新型硫化钨光热材料及其制备和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080280754A1 (en) * 2005-08-31 2008-11-13 Instituto Mexicano Del Petroleo Process For Preparing a Catalytic Composition For the Hydroconversion of Petroleum Fractions
WO2012031330A1 (fr) * 2010-09-10 2012-03-15 The University Of Queensland Catalyseur et procédé de production associé
US20140142206A1 (en) * 2011-07-08 2014-05-22 Saudi Basic Industries Corporation Carbon supported cobalt and molybdenum catalyst and use thereof for producing lower alcohols

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080280754A1 (en) * 2005-08-31 2008-11-13 Instituto Mexicano Del Petroleo Process For Preparing a Catalytic Composition For the Hydroconversion of Petroleum Fractions
WO2012031330A1 (fr) * 2010-09-10 2012-03-15 The University Of Queensland Catalyseur et procédé de production associé
US20140142206A1 (en) * 2011-07-08 2014-05-22 Saudi Basic Industries Corporation Carbon supported cobalt and molybdenum catalyst and use thereof for producing lower alcohols

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106238073A (zh) * 2016-07-15 2016-12-21 温州泓呈祥科技有限公司 一种MoS2/LDHS加氢脱硫催化剂的制备方法及应用
CN106238074A (zh) * 2016-07-15 2016-12-21 温州泓呈祥科技有限公司 一种Pt‑MoS2/LDHS加氢裂化催化剂的制备方法及应用
CN106277056A (zh) * 2016-07-27 2017-01-04 广东工业大学 一种氧掺杂MoS2纳米花的制备方法
CN114345374A (zh) * 2020-09-27 2022-04-15 武汉理工大学 一种碳布上构筑的非晶态多硫化钼析氢电催化剂的制备方法
CN114345374B (zh) * 2020-09-27 2024-03-08 武汉理工大学 一种碳布上构筑的非晶态多硫化钼析氢电催化剂的制备方法
CN114835163A (zh) * 2022-05-24 2022-08-02 南京邮电大学 一种面向水质净化的新型硫化钨光热材料及其制备和应用
CN114835163B (zh) * 2022-05-24 2023-07-21 南京邮电大学 一种面向水质净化的新型硫化钨光热材料及其制备和应用

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