# US 2013/0153468 A1 · Unsupported and supported non-promoted ruthenium sulfide catalyst with high catalytic activity for hydrocarbon hydrotreatments and its method

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- Number: US 2013/0153468 A1
- Document ID: US20130153468A1
- Status: Published application
- Kind: A1
- Application number: 13/444,411
- Filed: 2012-04-11
- Published: 2013-06-20
- Earliest claimed: 2011-12-14
- Assignees: Centro de Investigacion en Materiales Avanzados, S.C.
- Inventors: Carlos Elias Ornelas Gutierrez; Lorena Alvarez Contreras; Jose Rurik Farias Mancilla; Alfredo Aguilar Elguezabal
- Web page: https://patentgrep.com/patent/US20130153468A1

## CPC

- B01J 27/045: Platinum group metals
- B01J 35/613: {10-100 m2/g}
- B01J 35/615: {100-500 m2/g}
- B01J 35/77: Compounds characterised by their crystallite size
- B01J 37/0201: {Impregnation}
- B01J 37/031: {Precipitation}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/18: with gases containing free hydrogen
- B01J 37/20: Sulfiding
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C01G 55/00: Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C10G 3/44: {characterised by the catalyst used}
- C10G 45/04: characterised by the catalyst used
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2006/12: Surface area
- C01P 2006/17: Pore diameter distribution
- Y02P 30/20: using bio-feedstock
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention relates to a synthesis method for unsupported and supported ruthenium base (RuS2) catalysts from a ruthenium complex precursor, which is decomposed and activated by a simple activation process; these steps provide a catalyst with very high catalytic activity, in addition the incorporation of ruthenium complex precursor to a support by methods of incipient and wet impregnating is described; the obtained catalytic activities in this invention are in the order of 100 times the molybdenum sulfide catalyst without support and without promoter, 14 times the industrial supported catalyst, and 5 times the activity of the currently most active commercial unsupported catalyst.

## Claims

### Claim at position 1

1-8. (canceled)

### Claim 9

A synthesis method for obtaining ruthenium sulfide (RuS2) catalyst without an additional metal or not promoted comprising the steps of:
a) dissolving hydrated ruthenium chloride in a solution of R1COR2, R2-OH, C4H8O (THF), C4H8O2, CH2Cl2 (DCM), C2H3N (MeCN), C3H7ON (DMF), C2H6SO (DMSO) or a combination thereof:
wherein:
R1 is equal to OH or a lineal chain or branched radical C1 to C8;
R2 is equal to H, a lineal chain or branched radical C1 to C8, with relation 0.01 to 40 ml of solvent per gram of salt dissolved in methanol, ethanol or acetone;
b) dissolving ammonium chloride in solution of R1COR2, R2-OH, C4H8O (THF), C4H8O2, CH2Cl2 (DCM), C2H3N (MeCN), C3H7ON (DMF), C2H6SO (DMSO) or a combination of these;
wherein:
R1 is equal to OH or a lineal chain or branched radical C1 to C8;
R2 is equal to H, a lineal chain or branched radical C1 to C8, with relation 0.01 to 40 ml of solvent per gram of salt dissolved in water, methanol, ethanol, acetone or combination thereof;
c) adding the NH4Cl solution of b) in a molar relation of 1:1 to 10:1 to the ruthenium chloride solution of a), keeping in mechanical agitation between 100 to 700 rpm during the addition and up to 30 minutes after the addition has finished;
d) adding NH4OH or HCl in proportion of 0.01 to 2 ml per gram of ruthenium chloride;
e) adding to the solution of step c) or d) a R3COR4 or R3COOR5 compound,
wherein
R3 is a linear chain or branched radical C1 to C8,
R4 is equal to H or a linear chain or branched radical C1 to C8 and include 1 or 2 oxygen atoms or 1 nitrogen atom,
R5 is equal to a hydrogen radical or a linear chain or branched radical C1 to C10;
f) leaving to the solution of e) in mechanical agitation for 30 minutes between 100-700 rpm and resting from 0.1 to 3 hr to allow crystallization; a family of ruthenium complex compounds very soluble in water and sparingly soluble in acetone is produced and precipitated, the family of ruthenium complex compounds have decomposition temperatures above 200° C. and total decomposition to metallic ruthenium in inert atmosphere to temperatures lower than 415° C.; filtering and washing with acetone the precipitate;
g) incorporating the family of ruthenium complex compounds to a support by using a method selected from an incipient impregnating method or a wet impregnating method,
wherein a support bed includes: TiO2, zeolitic, MCM-41, SBA-15, alumina, silice, mixed oxides, or a combination thereof; doped or not doped, wherein the support bed is impregnated with a solution of the precursory complex in weight relation 1-90% of dissolved metallic charge in the minimum amount of solvent, wherein during the impregnation the solution of the ruthenium complex compounds is drip over the catalyst until filling all porosity; and
h) decomposing and activating the ruthenium precursor complex at temperatures between 350° C. to 550° C. with a heating rate from 2 to 50° C. per minute; under pressure of 1 atm, in a reducing atmosphere of a gas mixture formed by H2S/G where G may be H2, N2, Ar or He; in H2S concentrations from 2 to 99%.

### Claim 10 (depends on 9)

The synthesis method according to claim 9, wherein the method is carried out according to the following equation:
RuCl3+NH4Cl→RuNxH4xCl3+z+H2S→RuS2.

### Claim 11 (depends on 9)

The synthesis method according to claim 9, wherein the impregnation step uses a solvent selected from R1COR2, R2-OH, C4H8O (THF), C4H8O2, CH2Cl2 (DCM), C2H3N (MeCN), C3H7ON (DMF), C2H6SO (DMSO) or a combination thereof;
wherein
R1 is equal to OH, or a lineal chain or branched radical C1 to C8,
R2 is equal to H, or a lineal chain or branched radical C1 to C8, with relation 0.01 to 40 ml of solvent per gram of precursor dissolved in water, methanol, ethanol, acetone or one combination thereof.

### Claim 12 (depends on 9)

The synthesis method according to claim 9, wherein:
R3 is equal to a linear radical C1 to C2,
R4 is equal to a radical H or to a linear radical C1 to C2, and
R5 is equal to a radical H or to a linear radical C1 to C5 including 1 nitrogen atom or 2 oxygen atoms in relation of 0.5:1 to 20:1 in volume.

### Claim 13 (depends on 9)

The synthesis method according to claim 9, wherein the ruthenium complex compounds have conversions between 28 and 99%.

### Claim 14 (depends on 9)

A ruthenium sulfide catalysts not promoted, obtained by the method according to claims 9, wherein the ruthenium sulfide catalysts comprises a family of ruthenium precursory complex having the formula RuNxH4xCl3+Z, wherein X and Z have values from 0 to 10.

### Claim 15 (depends on 14)

The ruthenium sulfide catalysts according to claim 14, wherein the ruthenium sulfide catalyst is a unsupported catalyst with a superficial area from 40 to 250 m2/g, a high amount of active sites and low degree of crystallinity with crystals sizes of 2 to 50 nanometers.

### Claim 16 (depends on 9)

The synthesis method according to claim 9, wherein the ruthenium sulfide precursor is decomposed and is activated by the passage of h).

### Claim 17 (depends on 9)

The synthesis method according to claim 9, wherein the method provides unsupported and supported catalysts.

### Claim 18 (depends on 9)

The synthesis method according to claim 9, wherein the catalyst is incorporated to the support after step g.

### Claim 19 (depends on 9)

The use of ruthenium sulfide catalysts (RuS2) obtained by the method of claim 9, wherein the ruthenium sulfide catalysts are used in reactions of hydrotreating or hydroprocessing (HDT) of hydrocarbons, hydrodesulfuration, hydrodenitrogenation, or hydrodeoxigenation.