Title: Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith

Abstract

New amorphous molybdenum/tungsten sulfides with the general formula M.sup.n+.sub.2x/n (L.sub.6 S.sub.8)S.sub.x, where L is molybdenum or tungsten and M is a ternary metal, has been developed. Characterization of these amorphous materials by chemical and spectroscopic methods (IR, Raman, PES) shows that the (M.sub.6 S.sub.8).sup.0 cluster units are present. Vacuum thermolysis of the amorphous Na.sub.2x (Mo.sub.6 S.sub.8)S.sub.x .multidot.yMeOH first produces poorly crystalline NaMo.sub.6 S.sub.8 by disproportionation at 800.degree. C. and well-crystallized NaMo.sub.6 S.sub.8 at .gtoreq. 900.degree. C. Ion-exchange of the sodium material in methanol with soluble M.sup.2+ and M.sup.3+ salts (M=Sn, Co, Ni, Pb, La, Ho) produces the M.sup.n+.sub.2x/n (Mo.sub.6 S.sub.8)S.sub.x .multidot.yMeOH compounds. Additionally, the new reduced ternary molybdenum sulfides with the general formula M.sup.n+.sub.2x/n Mo.sub.6 S.sub.8+x (MeOH).sub.y ›MMOS! (M=Sn, Co, Ni) is an effective hydrodesulfurization (HDS) catalyst both as-prepared and after a variety of pretreatment conditions. Under specified pretreatment conditions with flowing hydrogen gas, the SnMoS type catalyst can be stabilized, and while still amorphous, can be considered as "Chevrel phase-like" in that both contain Mo.sub.6 S.sub.8 cluster units. Furthermore, the small cation NiMoS and CoMoS type pretreated catalyst showed to be very active HDS catalysts with rates that exceeded the model unpromoted and cobalt-promoted MoS.sub.2 catalysts.

Inventors:

Hilsenbeck, Shane J ^[1]; McCarley, Robert E ^[1]; Schrader, Glenn L ^[1]; Xie, Xiaobing ^[2]

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+ Show Inventor Affiliations

1. Ames, IA
2. College Station, TX

Issue Date:

Fri Jan 01 00:00:00 EST 1999

Research Org.:

Ames Laboratory (AMES), Ames, IA; Iowa State Univ., Ames, IA (United States)

OSTI Identifier:

872156

Patent Number(s):

5872073

Application Number:

08/694,907

Assignee:

United States of America as represented by United States (Washington, DC)

Patent Classifications (CPCs):

B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

C - CHEMISTRY C01 - INORGANIC CHEMISTRY C01G - COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F

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B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

B01J27/045 - Platinum group metals
B01J27/051 - Molybdenum
B01J27/0515 - {with iron group metals or platinum group metals}

C - CHEMISTRY C01 - INORGANIC CHEMISTRY C01G - COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F

C01G1/12 - Sulfides
C01G39/006 - {Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen}
C01G41/006 - {Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen}

C - CHEMISTRY C01 - INORGANIC CHEMISTRY C01P - INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

C01P2002/02 - Amorphous compounds
C01P2002/77 - by unit-cell parameters, atom positions or structure diagrams
C01P2002/82 - by IR- or Raman-data
C01P2002/85 - by XPS, EDX or EDAX data
C01P2006/12 - Surface area
C01P2006/60 - Optical properties, e.g. expressed in CIELAB-values
C01P2006/80 - Compositional purity

C - CHEMISTRY C10 - PETROLEUM, GAS OR COKE INDUSTRIES C10G - CRACKING HYDROCARBON OILS

C10G45/04 - characterised by the catalyst used

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DOE Contract Number:  

W-7405-ENG-82

Resource Type:

Patent

Country of Publication:

United States

Language:

English

Subject:

reduced; ternary; molybdenum; tungsten; sulfides; hydroprocessing; catalysis; therewith; amorphous; formula; 2x; metal; developed; characterization; materials; chemical; spectroscopic; methods; raman; pes; cluster; units; vacuum; thermolysis; na; multidot; ymeoh; produces; poorly; crystalline; namo; disproportionation; 800; degree; well-crystallized; gtoreq; 900; ion-exchange; sodium; material; methanol; soluble; salts; pb; compounds; additionally; meoh; mmos; effective; hydrodesulfurization; hds; catalyst; as-prepared; variety; pretreatment; conditions; specified; flowing; hydrogen; gas; snmos; type; stabilized; considered; chevrel; phase-like; contain; furthermore; cation; nimos; comos; pretreated; active; catalysts; rates; exceeded; model; unpromoted; cobalt-promoted; amorphous materials; hydrogen gas; reduced ternary; molybdenum sulfide; ternary metal; ternary molybdenum; molybdenum sulfides; chevrel phase; tungsten sulfides; treated catalyst; spectroscopic method; amorphous material; /502/208/423/