# US 9,040,447 B2 · Hydroprocessing catalysts and methods for making thereof

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- Number: US 9,040,447 B2
- Document ID: US9040447B2
- Status: Granted
- Kind: B2
- Application number: 13/331,690
- Filed: 2011-12-20
- Published: 2012-07-05
- Granted: 2015-05-26
- Earliest claimed: 2010-12-30
- Assignees: Chevron U.S.A. Inc.
- Applicants: Oleg Mironov; Alexander E. Kuperman
- Inventors: Oleg Mironov; Alexander E. Kuperman
- Web page: https://patentgrep.com/patent/US9040447B2

## CPC

- B01J 23/883: and nickel
- B01J 23/24: Chromium, molybdenum or tungsten
- B01J 23/85: Chromium, molybdenum or tungsten
- B01J 23/8872: {Alkali or alkaline earth metals}
- B01J 23/8873: {Zinc, cadmium or mercury}
- B01J 27/051: Molybdenum
- B01J 27/0515: {with iron group metals or platinum group metals}
- B01J 35/396: {Distribution of the active metal ingredient}
- B01J 37/20: Sulfiding
- C10G 49/04: containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
- C10G 49/06: containing platinum group metals or compounds thereof
- C10G 49/12: suspended in the oil, e.g. slurries
- B01J 35/615: {100-500 m2/g}
- B01J 35/617: {500-1000 m2/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/638: {more than 1.0 ml/g}
- B01J 35/695: {polymodal}
- C10G 2300/107: Atmospheric residues having a boiling point of at least about 538 °C
- C10G 2300/1077: Vacuum residues
- C10G 2300/205: Metal content
- C10G 2300/301: Boiling range
- C10G 2300/701: Use of spent catalysts
- C10G 2300/703: Activation
- C10G 2300/802: Diluents
- Y02P 10/20: Recycling
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A process for making an improved slurry catalyst for the upgrade of heavy oil feedstock is provided. In the process, a metal precursor solution comprising at least a water-soluble molybdenum compound and a water-soluble metal zinc compound is mixed under high shear mixing conditions to generate an emulsion. The emulsion is subsequently sulfided with a sulfiding agent ex-situ, or in-situ in a heavy oil feedstock to form the slurry catalyst. The in-situ sulfidation in heavy oil is under sufficient condition for the heavy oil feedstock to generate the sulfiding source needed for the sulfidation.

## Claims

### Claim 1

A process for preparing a slurry catalyst for use in upgrading a heavy oil feedstock, comprising:
providing a metal precursor solution comprising at least a water-soluble molybdenum compound and a water-soluble metal zinc compound in water;
mixing the metal precursor solution with a hydrocarbon diluent under sufficiently high shear mixing to generate an emulsion with droplet sizes ranging from 0.1 to 300 μm;
sulfiding the emulsion with at least a sulfiding agent to form a slurry catalyst having a particle size ranging from 1 to 300 μm;
wherein the emulsion is subjected to reduction at a temperature above ambient either before or after the sulfiding step; and
wherein the zinc compound is present in the slurry catalyst in a sufficient amount for a zinc to molybdenum weight ratio ranging from 1:10 to 10:1.

### Claim 2 (depends on 1)

The process of claim 1, wherein the emulsion is mixed with the heavy oil feedstock in a reactor under in-situ sulfiding condition for the heavy oil feedstock to provide the sulfiding agent needed for to sulfide the emulsion forming the slurry catalyst.

### Claim 3 (depends on 2)

The process of claim 2, wherein the in-situ sulfiding condition is at a temperature from 752° F. to 1112° F. and a pressure from 1435 psig (10 MPa) to 3610 psig (25MPa).

### Claim 4 (depends on 1)

The process of claim 1, where the sulfidation of the emulsion forming the slurry catalyst occurs ex-situ prior to the heavy oil upgrade.

### Claim 5 (depends on 4)

The process of claim 4, wherein the sulfiding agent is selected from the group of elemental sulfur, hydrogen sulfide, ammonium sulfide, ammonium polysulfide ([(NH4)2Sx), ammonium thiosulfate ((NH4)2S203), sodium thiosulfate Na2S203), thiourea CSN2H4, carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide (DMS), tertiarybutyl polysulfide (PSTB) and tertiarynonyl polysulfide (PSTN), and mixtures thereof.

### Claim 6 (depends on 4)

The process of claim 4, wherein the hydrocarbon diluent is selected from gasoline, diesel, vacuum gas oil, cycle oil, jet oil, fuel oil, heavy oil feedstock, and mixtures thereof.

### Claim 7 (depends on 4)

The process of claim 4, wherein a sufficient amount of sulfiding agent is provided a molar ratio of sulfur to molybdenum of at least 1.5 to 1 to sulfide the emulsion to form the slurry catalyst.

### Claim 8 (depends on 1)

The process of claim 1, wherein the hydrocarbon diluent comprises a mixture of heavy oil feedstock and at least one of a VGO, MCO, HCO, and mixtures thereof.

### Claim 9 (depends on 1)

The process of claim 1, wherein the emulsion comprises droplets having a size of 0.5 to 200 μm.

### Claim 10 (depends on 1)

The process of claim 1, wherein the emulsion comprises droplets having a size of less than 100 μm.

### Claim 11 (depends on 1)

The process of claim 1, wherein providing a metal precursor solution comprising at least a water-soluble molybdenum compound and a water -soluble metal zinc compound in water comprises providing a solution having a concentration of molybdenum in solution of less than 10 wt. %.

### Claim 12 (depends on 1)

The process of claim 1, wherein the metal precursor solution comprising at least a water-soluble molybdenum compound and a water-soluble metal zinc compound in water has a concentration of zinc in solution of less than 10 wt. %.

### Claim 13 (depends on 1)

The process of claim 1, wherein the metal precursor solution comprising at least a water-soluble molybdenum compound and a water-soluble metal zinc compound in water has pH of at least 4.

### Claim 14 (depends on 1)

The process of claim 1, wherein the slurry catalyst prepared therefrom has a total surface area of at least 100 m2/g.

### Claim 15 (depends on 1)

The process of claim 1, wherein the slurry catalyst prepared therefrom has a has a total pore volume of at least 0.4 cc/g and a polymodal pore distribution with at least 70% of pore sizes in the range of 5 to 1,000 Angstroms in diameter.

### Claim 16

A process for preparing a slurry catalyst for use in upgrading heavy oil feedstock, comprising:
providing a metal precursor solution comprising at least a water-soluble molybenum salt selected from molybdates, alkali metal heptamolybdates, alkali metal orthomolybdates, alkali metal isomolybdates, phosphomolybdic acid, molybdenum oxide, molybdenum carbide, molybdenum nitride, aluminum molybdate, molybdic acid, and mixtures thereof, and a water -soluble zinc salt, at a zinc to molybdenum weight ratio ranging from 1:30 to 5:1;
mixing the metal precursor solution with a hydrocarbon diluent under high shear mixing and under reducing conditions to generate an emulsion comprising droplets having a size of 0.1to 300 μm, the hydrocarbon diluent selected from gasoline, diesel, vacuum gas oil (VGO), cycle oil (MCO or HCO), jet oil, fuel oil, heavy oil feedstock, and mixtures thereof;
mixing the emulsion with at least a heavy oil feedstock under in-situ sulfiding conditions for the heavy oil feedstock to provide at least a sulfiding agent to sulfide the emulsion forming a slurry catalyst.

### Claim 17 (depends on 16)

The process of claim 16, wherein the emulsion is mixed with the heavy oil feedstock at a temperature from 752° F. to 1112° F. under a pressure from 1435 psig (10MPa) to 3610 psig (25 MPa) for in-situ sulfiding to take place.

### Claim 18 (depends on 16)

The process of claim 16, wherein the slurry catalyst prepared therefrom has an average particle size ranging from 1 to 300 μm.